Conformational studies by far infrared and Raman spectra of gases

One of the major goals of conformational analysis is the calculation of the energy difference between two or more conformers, ΔE, as well as the energy necessary for interconversion. The calculation of these energy quantities is facilitated by using a potential function which describes the vibrational motion, or internal rotation (torsion), as a function of the dihedral angle, α. The potential function is called asymmetric because both the frame and top portions of the molecule have no symmetry element higher than a plane. The most common type of potential function where at least one of the minima coincides with the plane of symmetry is of the type: V(α) = $\text{1}\text{2}$ΣV_i(1 - cos iα). The kinetic energy term, F(α), is extremely complicated. In general, if the only data being used to calculate the potential function are torsional transitions, and if one continues within the boundary conditions of a one-dimensional problem, then a cosine expansion of F(α) should be adequate: F(α) = F₀ + ΣF_i cos iα. For those systems where there is an equilibrium between a planar form and two non-planar forms, V₃ is usually the predominant term. This is because V₃ represents a three maxima/three minima potential per 2π (360°) internal rotation. In a similar fashion, V₂ is found to be the predominant term in the potential function for a system consisting of two equivalent non-planar conformers. Several examples of our most recent studies are given where the potential function for interconversion of two conformers has been determined.     

Raman spectra of gases: X. Raman band contour of the v7 (E') fundamentalof PF5

The Raman band contour of the v₇ (E') fundamental of PF₅ in the gas phase was recorded with a spectral slitwidth of 1.5 cm^?1 Failure to observe excited state transitions under this resolution leads to a lower limit for the barrier to Berry pseudorotation of 5.7 kcal mole^?1. The experimental contour was compared with a computer generated contour which gave a Coriolis constant, 0.00 ≧ XXX₇ ≧ ?0.30, consistent with the calculated value from the sum rule.     

Raman spectra phthalocyanines

Raman spectra of amorphous phthalocyanine thin films have been studied. Theoretical and experimental correlations in polarization ratios are applied to vibrational assignments of symmetry species and to the problem of molecular orientation in thin solid films.     

Raman spectra of molecular crystals. Carbon disulphide

Raman and far-infrared spectra of polycrytalline CS₂ samples at 79 and 18°K are reported, with assignments of molecular and lattice modes. Observed frequencies are compared with those from lattice dynamics calculations based on atom-atom interactions.     

IR spectra of aqueous disperse systems adsorbed atmospheric gases: 1. Nitrogen

Spectral characteristics of (H₂O) _i , N₂(H₂O) _i , and (N₂)₂(H₂O) _i cluster systems, where 10≤i≤50, are studied in the 0 ≤ ε ≤ 3500 cm^?1 frequency range with the molecular dynamics method on the basis of a flexible molecule model. After nitrogen is captured by an aqueous disperse system, the absorption of the IR radiation by this system increases owing to the enhancement of intramolecular vibrations. In general, the reflection of the outer IR radiation by nitrated aqueous disperse systems is attenuated; however, when the nitrogen concentration increases twofold, there is a tendency toward an increase in the fraction of reflected radiation. As the nitrogen concentration in a system of water clusters rises, the power of radiation emitted by the system increases significantly and the number of electrons interacting with the outer IR radiation decreases.     

Ti2: accurate determination of the dissociation energy from matrix resonance Raman spectra and chemical interaction with noble gases

UV-visible and resonance Raman spectra of Ti(2) isolated in Ar, Kr, and Xe matrices at temperatures of 10 K were measured by using the 514 nm line of an Ar ion laser. The data show that the Ti(2) molecule interacts strongly with Xe, leading to a significant weakening of the Ti[bond]Ti bond strength. The f(Ti[bond]Ti) force constant decreases in the series Ar>Kr>Xe, from 232.8 Nm(-1) in Ar and 225.5 Nm(-1) in Kr to 199.7 Nm(-1) in Xe. Additional experiments in an Ar matrix containing 2 % of Xe indicate the formation of a molecule of the formula Ti(2)Xe. Our spectra for Ti(2) in an Ar matrix give evidence for several previously not observed members of the Stokes progression. The sum of experimental data allows for an improved estimation of the dissociation energy on the basis of a LeRoy-Bernstein-Lam analysis. A dissociation energy of 1.18 eV was derived from this analysis. The UV-visible data give evidence of the vibrational levels of an excited state of Ti(2).     

IR spectra of aqueous disperse systems adsorbing atmospheric gases: 2. Argon

The absorption, reflection, and scattering of IR radiation by aqueous ultradisperse systems that absorb argon are studied with the molecular dynamics method on the basis of a flexible molecule model. Both the real and imaginary parts of dielectric permittivity are substantially increased at frequencies corresponding to intramolecular vibrations of atoms when each cluster of aqueous system adsorbs one argon atom. This effect disappears for the real part and becomes weak for the imaginary part of dielectric permittivity when there are two argon atoms added per cluster. In the region of intramolecular frequencies, the absorption coefficient of aqueous disperse systems containing argon increases as well. The reflection coefficient of the systems of water clusters that absorbed argon decreases in the frequency region of vibrations of molecules and increases in a frequency range corresponding to intramolecular vibrations. The power of radiation generated by cluster systems at the expense of thermal energy increases considerably when there is one adsorbed argon atom per cluster and decreases with a twofold increase in the number of argon atoms in clusters.     

Raman and i.r. spectra of 3-sulfolene

Raman and i.r. spectra of 3-sulfolene have been recorded and studied in the solid and liquid states. A vibrational assignment of the observed frequencies is proposed on the basis of the depolarization ratios of the Raman bands and of the dichroic ratios of the i.r. bands.     

Resonance Raman spectra of n-methylthioacetamide

Rigorous resonance, as well as preresonance Raman spectra of N-methylthioacetamide and its N-deuterated compound are reported. The observed selectivity in the resonance intensity enhancement is discussed in relation to the potential energy distributions obtained by normal coordinate treatment. The structural change concerning the CN and CS bond lengths is suggested to accompany the π^* ← π electronic excitation.     

Raman spectra of inorganic ions

This paper contains the Raman spectra of 79 inorganic salts and sulphur which may be used as an aid in qualitative inorganic analyses. These were obtained some years ago by conventional Raman spectroscopy. No such collection exists and the order of the reference spectra is identical to those in a collection of IR spectra. A table of characteristic frequencies for 17 polyatomic ions is given. These data have increased relevance following the emergence of FT-Raman as a rapid and efficient modern technique.     

Raman spectra of titanium dioxide

First-order Raman spectra have been recorded at room temperature for the anatase and rutile phases of polycrystalline titanium dioxide using an argon ion laser as exciter. The high-temperature rutile phase was found to be stabilized at temperatures below 450°C. Anatase transforms to rutile phase at ～750°C. All the Raman active fundamentals predicted by group theory are observed.     

Raman spectra of chlorophyll forms

The Raman spectra of chlorophyll a (Chl) forms in aqueous poly(vinyl alcohol) (PVA) and in dimethyl sulfoxide (DMSO)—water mixtures were recorded at 457.9 nm excitation and their structures were characterized by comparison with the spectra of the following well-known chlorophyll forms: (1) monomers (Chl)₁ in the polar solvents of group (A), i.e., diethyl ether, tetrahydrofuran, acetone, N,N-dimethylformamide and DMSO, of which the oxygen atom is expected to coordinate to the central magnesium atom; (2) monomers (Chl)₁ in the polar solvents of group (B), i.e., methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, which are supposed to form a hydrogen-bond to the C₉=O group in addition to the coordination-bond to the Mg atom; (3) dehydrated aggregates (Chl)_n in dry non-polar solvents, i.e., carbon tetrachloride, n-hexane and n-octane; and (4) hydrated aggregates (Chl·2H₂O)_n in wet non-polar solvents, i.e., n-hexane and n-octane. The frequency of the C₉ = O stretching Raman line of each of the above chlorophyll forms was: (1) 1702—1680 cm⁻¹; (2) 1673—1668 cm⁻¹; (3) around 1655 cm⁻¹; (4) around 1645 cm⁻¹. The frequency proved to be a marker of intermolecular interaction of the Chl molecules. The spectral patterns in the 1650—700 cm⁻¹ region of (1), (2) and (3) were similar. However, the relative intensities of Raman lines of (4), which was ascribed to a one-dimensional, regular stacking of the Chl macrocycles, were quite different from those of (1)—(3).The chlorophyll form in PVA aqueous solution was identified as (Chl·2H₂O)_n by spectral comparison. The chlorophyll forms present in the DMSO—water mixtures were highly dependent on the DMSO content. It is suggested that (Chl)₁ having hydrogen-bonded H₂O should be present in 10% DMSO solution, and that a new chlorophyll form (Chl·DMSO)_n having (a) a stoichiometric intermolecular interaction with DMSO and (b) a regular stacking of the chlorophyll macrocycles, should be predominant in 50% DMSO aqueous solution.     

The Raman spectra of bromoform

In this work the Raman spectrum of bromoform is recorded at various temperatures in the pure compound and in solution in carbon tetrachloride and the features shown by some of the bands are considered in the light of previous spectroscopic data interpretations. In particular, the concentration dependent effects exhibited by the ν₅(e) vibrational mode suggest, by comparison with similar effects previously observed in chloroform and trichloromethyl fluoride, the existence, in the pure liquid at room temperature, of important intermolecular interactions.     

Raman spectra of some terpenes

Summary Investigation of Raman spectra indicates increase in the interaction between the double bonds as we pass from sylvestrene and isosylvestrene to sylveterpinolene and indicates that the character of the interaction in the last compound is more complex than in 1,3-butadiene and other similar conjugated systems.     

Modeling vibrational spectra using the self-consistent charge density-functional tight-binding method. I. Raman spectra

An extension of the self-consistent charge density-functional tight-binding (SCC-DFTB) method is presented that allows for calculating intensities of peaks in vibrational Raman spectra for very large molecules. The extension is based on a simple ansatz: an extra term, which describes interaction of an external electric field with induced atomic charges, is added to the SCC-DFTB energy expression. We apply the modified SCC-DFTB formalism for reproducing vibrational Raman spectra of 17 organic molecules. The calculated spectra are compared with experiment and with spectra obtained from density functional theory (DFT) calculations. We find that the SCC-DFTB method is capable of reproducing most of the features of experimental Raman spectra. Limitations and advantages of this approach are analyzed and suggestions for interpreting calculated SCC-DFTB Raman spectra are given.